路易斯酸对亚铁血红素-NO 片段的活化作用促进了与 NO 的 N-N 偶联反应生成 NO。
Lewis Acid Activation of the Ferrous Heme-NO Fragment toward the N-N Coupling Reaction with NO To Generate NO.
机构信息
Department of Chemistry and Biochemistry , University of Oklahoma , Norman , Oklahoma 73019 , United States.
Department of Chemistry and Chemical Biology , Stevens Institute of Technology , Castle Point on Hudson , Hoboken , New Jersey 07030 , United States.
出版信息
J Am Chem Soc. 2018 Mar 28;140(12):4204-4207. doi: 10.1021/jacs.7b13681. Epub 2018 Mar 15.
Abstract
Bacterial NO reductase (bacNOR) enzymes utilize a heme/non-heme active site to couple two NO molecules to NO. We show that BF coordination to the nitrosyl O-atom in (OEP)Fe(NO) activates it toward N-N bond formation with NO to generate NO. N-isotopic labeling reveals a reversible nitrosyl exchange reaction and follow-up N-O bond cleavage in the NO formation step. Other Lewis acids (B(CF) and K) also promote the NO coupling reaction with (OEP)Fe(NO). These results, complemented by DFT calculations, provide experimental support for the cis: b pathway in bacNOR.
摘要
细菌一氧化氮还原酶（bacNOR）利用血红素/非血红素活性位点将两个 NO 分子偶联到 NO 上。我们表明，BF 与（OEP）Fe（NO）中硝酰基 O-原子的配位激活了它与 NO 形成 N-N 键以生成 NO。N-同位素标记表明在 NO 形成步骤中存在可逆的硝酰基交换反应和随后的 N-O 键断裂。其他路易斯酸（B（CF）和 K）也促进了（OEP）Fe（NO）与 NO 的偶联反应。这些结果与密度泛函理论计算相结合，为 bacNOR 中的顺式：b 途径提供了实验支持。
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